Reduced hierarchy equations of motion approach with Drude plus Brownian spectral distribution: Probing electron transfer processes by means of two- dimensionalcorrelation spectroscopy

Abstract

We theoretically investigate an electron transfer (ET) process in a dissipative environment by means of two-dimensional (2D) correlation spectroscopy. We extend the reduced hierarchy equations of motion approach to include both overdamped Drude and underdamped Brownian modes. While the overdamped mode describes the inhomogeneity of a system in the slow modulation limit, the underdamped mode expresses the primary vibrational mode coupled with the electronic states. We outline a procedure for calculating 2D correlation spectrum that incorporates the ET processes. The present approach has the capability of dealing with system-bath coherence under an external perturbation, which is important to calculate nonlinear response functions for non-Markovian noise. The calculated 2D spectrum exhibits the effects of the ET processes through the presence of ET transition peaks along the $\Omega_1$ axis, as well as the decay of echo signals.